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CA3167391A1 - Light stabilizer mixture - Google Patents

Light stabilizer mixture Download PDF

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Publication number
CA3167391A1
CA3167391A1 CA3167391A CA3167391A CA3167391A1 CA 3167391 A1 CA3167391 A1 CA 3167391A1 CA 3167391 A CA3167391 A CA 3167391A CA 3167391 A CA3167391 A CA 3167391A CA 3167391 A1 CA3167391 A1 CA 3167391A1
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Canada
Prior art keywords
tert
hydrogen
compound
bis
independently
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CA3167391A
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French (fr)
Inventor
Tania Weyland
Gerard Lips
Sebastien Villeneuve
Manuele Vitali
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BASF SE
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BASF SE
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • A01G9/1407—Greenhouses of flexible synthetic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/132—Phenols containing keto groups, e.g. benzophenones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2410/00—Agriculture-related articles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Environmental Sciences (AREA)
  • Soil Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Greenhouses (AREA)
  • Laminated Bodies (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

A stabilizer mixture comprising a sterically hindered amine light stabilizer, a triazine UV absorber and a benzophenone UV absorber.

Description

Light stabilizer mixture Description The present invention relates to a stabilizer mixture comprising a sterically hindered amine light stabilizer, a triazine UV absorber and a benzophenone UV absorber, a com-position comprising an organic material, preferably an organic polymer, subject to deg-radation induced by light, heat, oxidation or the effect of agrochemical compounds, to an article made of said composition, preferably a greenhouse film cover, and to a method for stabilizing the aforementioned organic material.
In more detail, the present invention relates to a stabilizer mixture comprising the com-ponents (a), (b) and (c), wherein component (a) is at least one compound of the formula (A), ,N, H3C N"--<CH3 H3c>'N'-<CH3 N A4 ¨ a (A), wherein A1 is C2-Ci8alkylene, C5-C7cycloalkylene or Ci-a4alkylenedi(C5-C7cycloal-kylene), the radicals A2 independently of one another are hydrogen, Ci-Cualkyl, Ci-Ci2alkyloxy, C5-Ci2cycloalkyl or C5-Ci2cycloalkyloxy, A3 and A4 independently of one another are hydrogen, Ci-Cualkyl, C5-C12cycloalkyl or a group of the formula (a-1), H3c c H3 N _________________________ A2 /

(a-1)
2 or the radicals A3 and A4, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, and a is a number from 1 to 20 and the repeating units are identical or different;

component (b) is at least one compound selected from the formulae (B-I) and (B-II), 0 _________________________________________________ OH
N N
Olt (B-I), wherein E2, E3, E4 and E5 independently of one another are hydrogen, Ci-Cisalkyl, phenyl or phenyl substituted by 1, 2 or 3 Cl-C4alkyl;
n is 1 0r2, when n is 1, El is Ci-Ci8alkyl, or 02-Cighydroxyalkyl which is interrupted by oxygen, and when n is 2, E1 is a bridging group of formula -CH2CH2-0-C(0)-(CH2)10-C(0)-0-CH2CH2-, 9¨Q1 T1 _________________________________ OH N 'N 0 02 J.
N
'><
Q3 __ 0 T3 T2 0 __ Q4 (B-II), wherein Qi, Qz, Q3 and Qa are independently of one another hydrogen, Cl-Cisalkyl, Ci-Ci8alkyl substituted by hydroxy, or C2-Ci8alkyl or C2-Ci8hydroxyalkyl interrupted by
3 oxygen, and T1, T2 and T3 are independently from each other hydrogen or Ci-Ci8alkyl;
and component (c) is a compound of formula (C) H
C =
CoH17 (C), and wherein the weight ratio of component (b) to (c) is 1:50 to 50:1.
Examples of alkyl having up to 18 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-nnethylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-nnethylheptyl, 3-methylheptyl, n-octyl, 2-ethyhhexyl, 1,1,3-trinnethylhexyl, 1,1,3,3-tetra-nnethylpentyl, nonyl, decyl, undecyl, 1-nnethylundecyl, dodecyl, 1,1,3,3,5,5-hexa-nnethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.
An example for C2-Ci8hydroxyalkyl which is interrupted by oxygen is the group of formula -CH2-CH(OH)-CH2-0-CH2-CH(02H5)-(CH2)3-CH3.
Examples of Ci-Ci2alkyloxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobu-toxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy and decyloxy. Cl-Csalkyloxy, in par-ticular propoxy, is preferred.
Examples of 05-C12cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cy-clododecyl.
Examples of C5-Ci2cycloalkyloxy are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooc-toxy, cyclodecyloxy and cyclododecyloxy. Cyclohexoxy is preferred.
A preferred examples of phenyl substituted by 1, 2 or 3 Cl-C4alkyl is 2,4-dimethylphenyl.
Examples of 02-Ci8alkylene are ethylene, propylene, trinnethylene, tetrannethylene, pen-tannethylene, 2,2-dinnethyltrinnethylene and hexannethylene.
4 An example of C5-C7cycloalkylene is cyclohexylene.
An example of C1-C4alkylenedi(C5-C7cycloalkylene) is nnethylenedicyclohexylene.
Where the radicals A3 and A4, together with the nitrogen atom to which they are bonded, form a 5-to 10-membered heterocyclic ring, this ring is for example 1-pyrrolidyl, piperi-dino, 1-piperazinyl, 4-methyl-1-piperazinyl, 1-hexahydroazepinyl, 5,5,7-trinnethy1-1-honnopiperazinyl or 4,5,5,7-tetrannethy1-1-honnopiperazinyl.
In the compounds of the formula (A) the terminal group attached to the diannino residue is for example hydrogen or a group of the formula A3 NI _______________ A4 1,1 A3_1\I
and the terminal group attached to the triazine radical is for example a group of the for-mula ________________________ A1 __ N __ H
H3C .11.CH H3C >n<CI I 3 H3C N CH 3 H3c N CH 3 __ A3_N
AI, AI, A2 or a group of the formula The stabilizer mixtures wherein wherein A1 is 02-Ci8alkylene, 05-C7cycloalkylene or Ci-C4alkylenedi(05-C7cycloal-kylene), the radicals A2 independently of one another are hydrogen, Ci-Cualkyl, Ci-Ci2alkyloxy, C5-Cucycloalkyl or C5-Cucycloalkyloxy, A3 and A4 independently of one another are hydrogen, C1-C12alkyl, C5-C12cycloalkyl or a group of the formula (a-1), and a is a number from 1 to 20 and the repeating units are identical or different.
The stabilizer mixtures wherein Ai is C2-C8alkylene or cyclohexylene, the radicals A2 independently of one another are hydrogen, Ci-C8alkyl, Ci-Ci2alkyloxy, cyclohexyl or cyclohexyloxy, A3 and A4 independently of one another are hydrogen, Ci-C8alkyl or a group of the for-mula (a-1), and a is a number from 1 to 10, are preferred.
5 Compounds of formula (B-I), wherein E2, E3, E4 and E5 are independently from each other hydrogen, Ci-C4alkyl or phenyl are preferred. More preferably, n is 1 and E1 is Ci-Cioalkyl.
Compounds of formula (B-II), wherein Qi, Q2, Q3 and Q4 are independently from each other hydrogen or Ci-Cioalkyl, and Ti, T2 and T3 are independently from each other hydrogen or Ci-C4alkyl are preferred.
As to component (b) compounds of formula (B-I) are preferred.
The following compounds of formula (A) are preferred:
H2C4 N __ rT'(CH 216 N __________ N
N N N N
HH:C H 3 .).õ...H3c.,,N,,,cH HH:cC H r CH
CH 3 Hoc. N 3 1-13C
1 AL2 A2 A, A2 H30CH H C CH , H33 C ---.<CH 3 Al2 (A-0) wherein 1 or 2 of the radicals A2 are hydrogen and the remaining radicals A2 are propyloxy, H9C4 N __ 1 ___________ (CH 2)6N ___ N C4H, H3C CHr H C CH HC CH , H3C>.'N''¨'CH 3 9 3 H3C 31),,N¨C4F19 H3C > N----<CH 3 Ft 1-1 H3C CH H C CH, H3C >N CH, 12133 C ">.'"N H 3 (A-1)
6 N N
1 H904 _N _____________________________ (CH 2)6 ___ N _______ r.-...- --.1 N_C,H9 ,-L N
, r= 1 __ ....y....,, -'.. r...,1 N ..__ N )\
I
CH 3 H H3C ,.........CH 3 H3C CH 3 ---r-N C4I-1, H30>, ,<CH3 H,C
H 3 C .-"N -.'"<CH 3 9C 1-N ......1.....: 3 C ""*.--"Ni '''CH 3 H 3 C NI
CH 3 ,.....õLõ.. - H3C NI CH 3 03H7 H3C>7.,N...."<cH 3 C31-17 3 7 H3C><"CH , I I

I

(A-2) _______________________ N __ (CH2)6 __ N __ N )\1 ---...--,--H3C 'N' CH3 1-13o-N"--- CH3 N ____________________ \N¨H
I I
H H I \ __ /
/
C4H9 Hsc C H3 ¨a (A-3) wherein a is a number from 1 to 20, for example 1 to 10, 2 to 20 or 2 to 10;
¨ r.....).N...,....ii ______________________ N __ (CH 2)6 __ N
N N

H 3 C >'N --'<CH 3 H 3 0 .." N ---<C H 3 N ___ Y
, , ( N ¨0 ¨C 3H 2 0 0 I __ /
I I C4H9 H3c CH 3 03H7 03H7 ¨ d (A-4) wherein a is a number from 1 to 20, for example 1 to 10, 2 to 20 or 2 to 10.
The following compounds are preferred for formulae (B-I) and (B-II):
o¨CHCH¨C4H9-n N'" N
I (B-1) .
N
7 0-C61-1,3-n OH
N N
4110 N 411 (B-2) OH
N N (B-3) H,C N
CH, H,C 41 CH, . - =
OH
= N
=
.fit; - -(B-4) , OH
_ .11 r I
(B-5)
8 C)C) = OH
N
Nr (B-6) OH N `NI OH
'N
(B-7).
Highly preferred are those of formulae (B-1), (B-2) and (B-3).
Most of the compounds of the formulae (A) and (B) are known and can be prepared in analogy to processes known to those skilled in the art.
The compounds of the formula (A) can be prepared for example in analogy to the meth-ods described in US-A-4,997,938, US-A-5,116,893, US-B-8,895,647, US-A-6,046,304, US-A-6117995, US-B-6420462 and US-B-6677451.
The compounds of the formula (B) can be prepared for example in analogy to the meth-ods described in US-B-6,255,483.
The compounds of formula (C) are commercially available as Chinnassorb0 81 from BASF SE.
The weight ratio of component (a) to (b) is 50:1 to 24:1, preferably 45:1 to 24:1, more preferably 40:1 to 24:1, most preferably 37:1 to 24:1.
9 The weight ratio of component (b) to (c) is preferably 1:25 to 25:1, more preferably 1:25 to 5:1 and especially 1:25 to 1:1. Highly preferred is a ratio of 1:20 to 1:2, especially 1:15 to 1:2.
The weight ratio of component (a) to the sum of the weight of components (b) and (c) is preferably 1:10 to 50:1, more preferably 1:5 to 50:1, especially 1:2 to 40:1.
Highly pre-ferred is a ratio of 1:2 to 40:1, especially 1:1 to 40:1.
According to a further embodiment the weight ratio of component (a) to the sum of the weight of components (b) and (c) is preferably 1:1 to 20:1.
The weight ratio of component (a) to (c) is preferably 1:10 to 40:1, more preferably 1:5 to 30:1, especially 1:2 to 20:1. Highly preferred is a ratio of 1:1 to 20:1, especially 2:1 to 20:1.
According to a further preferred embodiment the stabilizer mixture additionally contains a component (d) which is at least one compound selected from the formulae (D-1) and (D-2).
H3c CH3 H3C __ C CH2 0 N 0 C Ci7H35 (D-1) N (D-2) 0 N __ 01-12 CH2 000 CH2CH2 CO

b wherein b is a number from 2 to 20.
The weight ratio of components (a) to (d) is preferably 20:1 to 1:1.
The weight ratio of the sum of the weight of components (a) and (d) to component (b) is 50:1 to 24:1, preferably 45:1 to 24:1, more preferably 40:1 to 24:1, most preferably 37:1 to 24:1.

In the compound of the formula (D-2) the end group attached to the oxygen is for exam-ple hydrogen and the end group attached to the ¨CO- group is for example -0-Ci-C3alkyl depending on the preparation.
5 Another embodiment of the present invention is a composition containing (I) an organic material, preferably an organic polymer, in particular a polyolefin, subject to degradation induced by light, heat, oxidation or agrochemical compounds and (II) a stabilizer mixture as defined above.
Examples of the organic material to be stabilized are 1. Polymers of nnonoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-nnethylpent-1-ene, polyvinylcyclohexane, polyisoprene or poly-butadiene, as well as polymers of cycloolefins, for instance of cyclopentene or nor-bornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), me-dium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of nnonoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerisation (normally under high pressure and at elevated tempera-ture).
b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either 7C-or 0-coordinated. These metal complexes may be in the free form or fixed on sub-strates, typically on activated magnesium chloride, titanium(III) chloride, alu-mina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said met-als being elements of groups la, Ila and/or IIla of the Periodic Table. The acti-vators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), nnetallocene or single site catalysts (SSC).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of nnonoolefins and diolefins with each other or with other vinyl mono-mers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/nnethylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, eth-ylene/cycloolefin copolymers (e.g. ethylene/norbornene like COC), ethylene/1-olefins co-polymers, where the 1-olefin is generated in-situ; propylene/butadiene copolymers, iso-butylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl nnethacrylate copolymers, ethylene/vinyl acetate co-polymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as ter-polymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copoly-mers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid co-polymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/car-bon monoxide copolymers and mixtures thereof with other polymers, for example poly-amides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
Honnopolynners and copolymers from 1.) - 4.) may have any stereostructure including syndiotactic, isotactic, henni-isotactic or atactic; where atactic polymers are preferred.
Stereoblock polymers are also included.

5. Polystyrene, poly(p-nnethylstyrene), poly(oc-nnethylstyrene).
6. Aromatic honnopolynners and copolymers derived from vinyl aromatic monomers in-cluding styrene, oc-nnethylstyrene, all isomers of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Honnopolynners and copolymers may have any stere-ostructure including syndiotactic, isotactic, henni-isotactic or atactic;
where atactic poly-mers are preferred. Stereoblock polymers are also included.
6a. Copolymers including aforementioned vinyl aromatic monomers and connononners selected from ethylene, propylene, dienes, nitriles, acids, nnaleic anhydrides, malei-nnides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene (interpolynners), sty-rene/alkyl nnethacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl meth-acrylate, styrene/nnaleic anhydride, styrene/acrylonitrile/methyl acrylate;
mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolynner; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/eth-ylene/butylene/styrene or styrene/ethylene/propylene/styrene.
6b. Hydrogenated aromatic polymers derived from hydrogenation of polymers men-tioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydro-genating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers men-tioned under 6a.).
Honnopolynners and copolymers may have any stereostructure including syndiotactic, isotactic, henni-isotactic or atactic; where atactic polymers are preferred.
Stereoblock pol-ymers are also included.
7. Graft copolymers of vinyl aromatic monomers such as styrene or oc-nnethylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or nnethacrylonitrile) on polybutadiene;
styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and nnaleic anhydride on polybutadiene; styrene, acrylonitrile and nnaleic anhydride or nnaleinnide on polybutadiene; styrene and nnaleinnide on polybutadiene; styrene and alkyl acrylates or nnethacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolynners; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl nnethacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorin-ated and bronninated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin honno- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from oc,8-unsaturated acids and derivatives thereof such as poly-acrylates and polynnethacrylates; polynnethyl nnethacrylates, polyacrylannides and poly-acrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/al-kyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide co-polymers or acrylonitrile/ alkyl nnethacrylate/butadiene terpolynners.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, pol-yvinyl benzoate, polyvinyl nnaleate, polyvinyl butyral, polyallyl phthalate or polyallyl mel-amine; as well as their copolymers with olefins mentioned in 1) above
12. Homopolynners and copolymers of cyclic ethers such as polyalkylene glycols, poly-ethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a connononner; polyacetals modified with thermoplastic polyurethanes, acrylates or M BS.
14 14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with sty-rene polymers or polyannides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybuta-dienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyannides and copolyannides derived from diannines and dicarboxylic acids and/or from anninocarboxylic acids or the corresponding lactanns, for example polyannide 4, pol-yannide 6, polyannide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyannide 11, polyannide 12, aro-matic polyannides starting from m-xylene diannine and adipic acid; polyannides prepared from hexannethylenediannine and isophthalic or/and terephthalic acid and with or without an elastonner as modifier, for example poly-2,4,4,-trinnethylhexannethylene tereph-thalannide or poly-m-phenylene isophthalannide; and also block copolymers of the afore-mentioned polyannides with polyolefins, olefin copolymers, iononners or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypro-pylene glycol or polytetrannethylene glycol; as well as polyannides or copolyannides mod-ified with EPDM or ABS; and polyannides condensed during processing (RIM
polyannide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhy-dantoins and polybenzinnidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones or lactides, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate and polyhydroxybenzoates as well as copolyether esters derived from hy-droxyl-terminated polyethers, and also polyesters modified with polycarbonates or MBS.
Copolyesters may comprise, for example - but are not limited to -polybutylenesuccin-ate/terephtalate, polybutyleneadipate/terephthalate, polytetrannethyleneadipate/tereph-thalate, polybutylensuccinate/adipate, polybutylensuccinate/carbonate, poly-3-hydroxy-butyrate/octanoate copolymer, poly-3-hydroxybutyrate/hexanoate/decanoate terpoly-nner. Furthermore, aliphatic polyesters may comprise, for example - but are not limited to - the class of poly(hydroxyalkanoates), in particular, poly(propiolactone), poly(butyro-lactone), poly(pivalolactone), poly(valerolactone) and poly(caprolactone), polyethylenesuccinate, polypropylenesuccinate, polybutylenesuccinate, polyhexanneth-ylenesuccinate, polyethyleneadipate, polypropyleneadipate, polybutyleneadipate, poly-hexannethyleneadipate, polyethyleneoxalate, polypropyleneoxalate, polybutyleneoxa-late, polyhexannethyleneoxalate, polyethylenesebacate, polypropylenesebacate, polybu-5 tylenesebacate and polylactic acid (PLA) as well as corresponding polyesters modified with polycarbonates or MBS. The term "polylactic acid (PLAY " designates a honno-poly-mer of preferably poly-L-lactide and any of its blends or alloys with other polymers; a co-polymer of lactic acid or lactide with other monomers, such as hydroxy-carboxylic acids, like for example glycolic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid, 4-hydroxy-10 valeric acid, 5-hydroxy-valeric acid, 6-hydroxy-caproic acid and cyclic forms thereof; the terms "lactic acid" or "Iactide" include L-lactic acid, D-lactic acid, mixtures and dinners thereof, i.e. L-Iactide, D-Iactide, nneso-lacide and any mixtures thereof.
19. Polycarbonates and polyester carbonates.
20. Polyketones.
21. Polysulfones, polyether sulfones and polyether ketones.
22. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and nnelannines on the other hand, such as phenol/formaldehyde resins, urea/formalde-hyde resins and melamine/formaldehyde resins.
23. Drying and non-drying alkyd resins.
24. Unsaturated polyester resins derived from copolyesters of saturated and unsatu-rated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
25. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
26. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aro-matic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A
and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
28. Natural polymers such as cellulose, rubber, gelatin and chemically modified homol-ogous derivatives thereof, for example cellulose acetates, cellulose propionates and cel-lulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
29. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Poly-annide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thernnoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
30. Naturally occurring and synthetic organic materials which are pure monomeric com-pounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g.
phthalates, adipates, phosphates or trinnellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aque-ous emulsions of such materials.
31. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
The organic material is preferably a polyolefin, more preferably a polyolefin selected from the group consisting of linear low density polyethylene, low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-butyl acrylate copoly-nner, and polypropylene honno- or copolymer.
The stabilizer mixture according to the present invention may be present in the organic material to be stabilized in an amount of preferably 0.005 to 10 % or 0.005 to 5 %, in particular 0.01 to 2.5 % or 0.05 to 2 %, relative to the weight of the organic material.

The individual components of the present stabilizer mixture may be added to the organic material to be stabilized either individually or mixed with one an-other. They can be added to a polymer before, during or after the polymeriza-tion or before or after the crosslinking.
The stabilizer composition according to the present invention or its individual compo-nents can be incorporated into the organic material to be stabilized by known methods, for example before or during shaping or by applying the dissolved or dispersed stabilizer to the organic material, if necessary with subsequent evaporation of the solvent. The stabilizers can be added to the organic material in the form of a powder, granules or a nnasterbatch, which contains said stabilizers in, for example, a concentration of from 2.5 to 90%, preferably 2.5 to 25%, by weight.
Examples of processing or transformation of the materials stabilized according to the present invention are:
Injection blow molding, extrusion, blow molding, rotonnolding, in mold decoration (back injection), slush molding, injection molding, co-injection molding, forming, compression molding, pressing, film extrusion (cast film; blown film), fiber spinning (woven, non-wo-ven), drawing (uniaxial, biaxial), annealing, deep drawing, calandering, mechanical transformation, sintering, coextrusion, coating, lamination, crosslinking (radiation, perox-ide, silane), vapor deposition, weld together, glue, vulkanization, thermoforming, pipe extrusion, profile extrusion, sheet extrusion; sheet casting, spin coating, strapping, foam-ing, recycling / rework, extrusion coating, visbreaking (peroxide, thermal), fiber melt blown, spun bonded, surface treatment (corona discharge, flame, plasma), sterilization (by gamma rays, electron beams), cast polymerization (R&M process, RAM
extrusion), gel-coating, tape extrusion, GMT-process, SMC-process, plastisol, and dipping (PVC, latex).
The stabilized material may additionally also contain various conventional additives, for example:
1. Antioxidants It t Alkylated nnonophenols, for example 2,6-di-tert-butyl-4-nnethylphenol, 2-tert-butyl-4,6-dinnethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopenty1-4-nnethylphenol, 2-(a-methylcyclohexyl)-4,6-dinnethylphenol, 2,6-dioctadecy1-4-nnethylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-buty1-4-nnethoxynnethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nony1-4-nnethylphenol, 2,4-dinnethy1-6-(1-nnethylundec-1-yOphenol, 2,4-dinnethy1-6-(1-nnethylheptadec-1-yOphenol, 2,4-dinnethy1-6-(1-methyl-tridec-1'-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylphenols, for example 2,4-dioctylthionnethy1-6-tert-butylphenol, 2,4-di-octylthionnethy1-6-nnethylphenol, 2,4-dioctylthiomethy1-6-ethylphenol, 2,6-d1-dodecylthi-onnethy1-4-nonylphenol.
1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-buty1-4-meth-oxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-annylhydroquinone, 2,6-dipheny1-4-octadecyloxyphenol, 2,6-d i-tert-butylhydroquinone, 2 ,5-d i-tert-butyl-4-hydroxyan isole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
1.4. Tocopherols, for example oc-tocopherol, 13-tocopherol, y-tocopherol, 6-tocopherol and mixtures thereof (vitamin E).
1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-buty1-4-nnethylphe-nol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-nnethylphenol), 4,4'-thiobis(6-tert-buty1-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethy1-4-hydroxyphenyl)disulfide.
1.6. Alkylidenebisphenols, for example 2,2'-nnethylenebis(6-tert-butyl-4-nnethylphenol), 2,2'-nnethylenebis(6-tert-butyl-4-ethylphenol), 2,2'-nnethylenebis[4-methy1-6-(a-methyl-cyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-meth-ylenebis(6-nony1-4-nnethylphenol), 2,2'-nnethylenebis(4,6-di-tert-butylphenol), 2,2'-ethyli-denebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2-nnethylenebis[6-(0c-nnethylbenzy1)-4-nonylphenol], 2,2'-nnethylenebis[640c,oc-dime-thylbenzy1)-4-nonylphenol], 4,4'-nnethylenebis(2,6-di-tert-butylphenol), 4,4'-meth-ylenebis(6-tert-buty1-2-nnethylphenol), 1,1-bis(5-tert-buty1-4-hydroxy-2-nnethylphenyl)bu-tane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzy1)-4-methylphenol, 1,1,3-tris(5-tert-buty1-4-hydroxy-2-nnethylphenyl)butane, 1,1-bis(5-tert-buty1-4-hydroxy-2-methyl-phe-ny1)-3-n-dodecylnnercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-buty1-4'-hydroxy-phenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-Z-hydroxy-5'-nnethylbenzy1)-6-tert-buty1-4-nnethylphenyllterephthalate, 1,1-bis-(3,5-dinnethy1-2-hydroxyphenyl)butane, 2 ,2-bis(3 ,5-d i-tert-butyl-4-hyd roxyphe-nyl)propane, 2,2-bis(5-tert-buty1-4-hydroxy2-nnethylpheny1)-4-n-dodecylnnercaptobu-tane, 1,1,5,5-tetra-(5-tert-buty1-4-hydroxy-2-nnethylphenyl)pentane.
1.7. 0-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-buty1-4,4'-dihy-droxydibenzyl ether, octadecy1-4-hydroxy-3,5-dinnethylbenzylnnercaptoacetate, tridecy1-4-hydroxy-3,5-di-tert-butylbenzylnnercaptoacetate, tris(3,5-di-tert-buty1-4-hydroxyben-zypannine, bis(4-tert-buty1-3-hydroxy-2,6-dinnethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isoocty1-3,5-di-tert-buty1-4-hydroxybenzylnne rcapto-acetate.
1.8. Hydroxybenzylated nnalonates, for example dioctadecy1-2,2-bis(3,5-di-tert-buty1-2-hydroxybenzyl)nnalonate, di-octadecy1-2-(3-tert-buty1-4-hydroxy-5-nnethylbenzyl)nnalo-nate, di-dodecylnnercaptoethy1-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyOnnalonate, bis[4-(1,1,3,3-tetrannethylbutyl)pheny1]-2,2-bis(3,5-d i-tert-buty1-4-hydroxybenzyl)nnalo-nate.
1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris(3,5-di-tert-buty1-4-hy-droxybenzyI)-2,4,6-trinnethylbenzene, 1,4-bis(3,5-di-tert-buty1-4-hydroxybenzy1)-2,3,5,6-tetrannethylbenzene, 2,4,6-tris(3,5-di-tert-buty1-4-hydroxybenzyl)phenol.
1.10. Triazine compounds, for example 2,4-bis(octylnnercapto)-6-(3,5-di-tert-buty1-4-hy-droxyanilino)-1,3,5-triazine, 2-octylnnercapto-4,6-bis(3,5-di-tert-buty1-4-hydroxyanilino)-1,3,5-triazine, 2-octylnnercapto-4,6-bis(3,5-di-tert-buty1-4-hydroxyphenoxy)-1,3,5-tria-zine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-buty1-4-hydroxybenzypisocyanurate, 1,3,5-tris(4-tert-buty1-3-hydroxy-2,6-dimethylben-zypisocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-buty1-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexy1-4-hydroxybenzypisocyanurate.
1.11. Benzylphosphonates, for example dinnethy1-2,5-di-tert-buty1-4-hydroxyben-zylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecy13,5-di-tert-buty1-4-hydroxybenzylphosphonate, d ioctadecy1-5-tert-buty1-4-hyd roxy-3-nnethylbenzylphosphonate, the calcium salt of the nnonoethyl ester of 3,5-di-tert-buty1-4-hydroxybenzylphosphonic acid.

1.12. Acylanninophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbannate.
5 1.13. Esters of 13-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhy-dric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hex-anediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethy-lene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocy-anurate, N,N'-bis(hydroxyethyl)oxannide, 3-thiaundecanol, 3-thiapentadecanol, trinne-10 thylhexanediol, trinnethylolpropane, 4-hydroxymethy1-1-phospha-2,6,7-trioxabicy-clo[2.2.2]octane.
1.14. Esters of 13-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-15 hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodieth-ylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocy-anurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trime-thylhexaned iol, trinnethylolpropane, 4-hydroxymethy1-1-phospha-2,6,7-trioxabicy-clo[2.2.2]octane; 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-nnethylphenyl)propionyloxy}-1,1-20 dinnethylethyI]-2,4,8,10-tetraoxaspiro[5.5]undecane.
1.15. Esters of 13-(3,5-dicyclohexy1-4-hydroxyphenyl)propionic acid with mono-or poly-hydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, di-ethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyDoxannide, 3-thiaundecanol, 3-thiapentadecanol, trinnethylhexanediol, trimethylolpropane, 4-hydroxymethy1-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric al-cohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonane-diol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy-droxyethyl)oxannide, 3-thiaundecanol, 3-thiapentadecanol, trinnethylhexanediol, trinne-thylolpropane, 4-hydroxynnethy1-1-phospha-2,6,7-trioxabicyclo[2.2_2]octane.

1.17. Amides of 8-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert-buty1-4-hydroxyphenylpropionyl)hexannethylenediannide, N,N'-bis(3,5-di-tert-buty1-4-hydroxyphenylpropionyl)trinnethylenediannide, N,N'-bis(3,5-di-tert-buty1-4-hydroxy-phenylpropionyl)hydrazide, N, N'-bis[2-(3-[3,5-d i-tert-butyl-4-hydroxyphenyl] propio-nyloxy)ethyl]oxamide (Naugard XL-1, supplied by Uniroyal).
1.18. Ascorbic acid (vitamin C) 1.19. Anninic antioxidants, for example N,N'-di-isopropyl-p-phenylenediannine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dinnethylpentyI)-p-phenylenediamine, N,N'-bis(1-ethy1-3-nnethylpenty1)-p-phenylenediannine, N,N'-bis(1-nnethylheptyI)-p-phenylene-diannine, N,N'-dicyclohexyl-p-phenylenediannine, N,N'-diphenyl-p-phenylenediannine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediannine, N-(1,3-dinnethylbutyI)-N'-phenyl-p-phenylenediannine, N-(1-nnethylhepty1)4F-phenyl-p-phenylenediannine, N-cyclohexyl-N'-phenyl-p-phenylenediannine, 4-(p-toluenesul-fannoyDdiphenylannine, N,N'-dinnethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenyla-mine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylpheny1)-1-naphthylannine, N-phenyl-2-naphthylannine, octylated diphenyla-mine, for example p,p'-di-tert-octyldiphenylannine, 4-n-butylanninophenol, 4-butyryla-nninophenol, 4-nonanoylanninophenol, 4-dodecanoylanninophenol, 4-octadeca-noylanninophenol, bis(4-nnethoxyphenyl)annine, 2,6-di-tert-buty1-4-dinnethylannino-methylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetrannethy1-4,4'-dianninodiphenyInnethane, 1,2-bis[(2-nnethylphenyl)annino]ethane, 1,2-bis(phenylannino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dinnethylbutyl)phenyl]annine, tert-octylated N-phenyl-1-naphthylannine, a mixture of mono- and dialkylated tert-bu-tyl/tert-octyldiphenylannines, a mixture of mono- and dialkylated nonyldiphenylannines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dial-kylated isopropyl/isohexyldiphenylannines, a mixture of mono- and dialkylated tert-bu-tyldiphenylannines, 2,3-dihydro-3,3-dinnethy1-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono-and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-dianninobut-2-ene.
2. UV absorbers and light stabilizers 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-nnethylphenyI)-benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-buty1-2'-hy-droxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetrannethylbutyl)phenyl)benzotria-zole, 2-(3',5'-di-tert-buty1-2'-hydroxypheny1)-5-chloro-benzotriazole, 2-(3'-tert-buty1-2'-hy-droxy-5'-nnethylphenyI)-5-chloro-benzotriazole, 2-(3'-sec-buty1-5'-tert-buty1-2'-hydroxy-phenyObenzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyObenzotriazole, 2-(3',5'-di-tert-amy1-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(0c,oc-dinnethylbenzy1)-2'-hydroxy-phenyObenzotriazole, 2-(3'-tert-buty1-2'-hydroxy-5'-(2-octyloxycarbonylethyl)pheny1)-5-chloro-benzotriazole, 2-(3'-tert-buty1-5'-[2-(2-ethyl hexyloxy)-carbonylethyI]-2'-hyd roxy-phenyl)-5-chloro-benzotriazole, 2-(3'-tert-buty1-2'-hydroxy-5'-(2-nnethoxycarbon-ylethyl)pheny1)-5-chloro-benzotriazole, 2-(3'-tert-buty1-2'-hydroxy-5'-(2-nnethoxycarbon-ylethyl)phenyl)benzotriazole, 2-(3'-tert-buty1-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phe-nypbenzotriazole, 2-(3'-tert-buty1-5'42-(2-ethylhexyloxy)carbonylethy11-2'-hydroxy-phenyl)benzotriazole, 2-(3'-dodecy1-2'-hydroxy-5'-nnethylphenyl)benzotriazole, 2-(3'-tert-buty1-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetrannethylbuty1)-6-benzotriazole-2-ylphenol]; the transesterification prod-uct of 243'-tert-buty1-5'-(2-methoxycarbonylethyl)-2.-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R¨CH2CHcoo-cH2cH21 2 ,where R = 3'-tert-bu-tyl-4-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 242'-hyd roxy-3'-(oc,oc-d methyl benzyI)-5'-(1,1, 3,3-tetrannethylbutyI)-phenyl]benzotriazole ; 2-[2'-hyd roxy-3'-(1,1,3,3-tetra methyl-buty1)-5'-(oc,a-dinnethylbenzyl)-phenyllbenzotriazole.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-nnethoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dinnethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butyl-phe-nyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-buty1-4-hy-droxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-bu-ty1-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-buty1-4-hydroxyben-zoate.
2.4. Acrylates, for example ethyl cc-cyano-6,6-diphenylacrylate, isooctyl oc-cyano-3,13-diphenylacrylate, methyl oc-carbonnethoxycinnannate, methyl cc-cyano-13-methyl-p-methoxycinnamate, butyl cc-cyano-p-methyl-p-methoxy-cinnamate, methyl 0C-carbonnethoxy-p-nnethoxycinnannate, N-W-carbonnethoxy-f3-cyanoyiny0-2-nnethylindo-line, neopentyl tetra(cc-cyano-1343-diphenylacrylate.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis[4-(1,1,3,3-tetra-nnethylbutypphenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylannine, triethanolamine or N-cyclohexyldiethanolannine, nickel dibutyl-dithiocarbannate, nickel salts of the nnonoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoxinnes, e.g. of 2-hydroxy-4-nnethylphenylundecylketoxinne, nickel complexes of 1-pheny1-4-lauroy1-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example carbonic acid bis(1-undecyloxy-2,2,6,6-tet-rannethy1-4-piperidypester, bis(2,2,6,6-tetrannethy1-4-piperidyl)sebacate, bis(2,2,6,6-tet-rannethy1-4-piperidyl)succinate, bis(1,2,2,6,6-pentannethy1-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetrannethy1-4-piperidyl)sebacate, bis(1,2,2,6,6-pentannethy1-4-pi-peridyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylnnalonate, the condensate of 1-(2-hy-droxyethyl)-2,2,6,6-tetramethy1-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N.-bis(2,2,6,6-tetrannethy1-4-piperidyl)hexannethylenediannine and 4-tert-octylannino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetrannethy1-4-piperidyl)nitrilotri-acetate, tetrakis(2,2,6,6-tetrannethy1-4-piperidy1)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediy1)-bis(3,3,5,5-tetrannethylpiperazinone), 4-benzoy1-2,2,6,6-tetrannethylpi-peridine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidy1)-2-n-buty1-2-(2-hydroxy-3,5-di-tert-butylbenzyOnnalonate, 3-n-octy1-7,7,9,9-tetrannethy1-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetrannethylpiperidyl)se-bacate, bis(1-octyloxy-2,2,6,6-tetrannethylpiperidyl)succinate, linear or cyclic conden-sates of N,N'-bis(2,2,6,6-tetrannethy1-4-piperidyphexannethylenediamine and 4-nnorpho-lino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetrannethylpiperidy1)-1,3,5-triazine and 1,2-bis(3-anninopropylannino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylannino-1,2,2,6,6-pentannethylpiperidyI)-1,3,5-tri-azine and 1,2-bis(3-anninopropylamino)ethane, 8-acety1-3-dodecy1-7,7,9,9-tetrannethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecy1-1-(2,2,6,6-tetrannethy1-4-piperidyl)pyr-rolidine-2,5-dione, 3-dodecy1-1-(1,2,2,6,6-pentannethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetrannethylpiperidine, a conden-sate of N,N'-bis(2,2,6,6-tetrannethy1-4-piperidyl)hexannethylenediannine and 4-cyclohex-ylannino-2,6-dichloro-1,3,5-triazine, a condensate of 1,2-bis(3-anninopropylannino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylannino-2,2,6,6-tetrannethylpiperidine (CAS Reg. No. [136504-96-6]); a condensate of 1,6-hexanediannine and 2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and 4-butylannino-2,2,6,6-tetrannethylpiperi-dine (CAS Reg. No. [192268-64-7]); N-(2,2,6,6-tetrannethy1-4-piperidy1)-n-dodecylsuc-cininnide, N-(1,2,2,6,6-pentannethy1-4-piperidy1)-n-dodecylsuccininnide, 2-undecyl-7,7,9,9-tetrannethy1-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetrannethy1-2-cycloundecy1-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentannethy1-4-piperidyloxycarbony1)-2-(4-nnethoxy-phenypethene, N,N'-bis-fornnyl-N,N'-bis(2,2,6,6-tetrannethy1-4-piperidyl)hexannethylene-diannine, a diester of 4-nnethoxynnethylenennalonic acid with 1,2,2,6,6-pentannethy1-4-hy-droxypiperidine, poly[nnethylpropy1-3-oxy-4-(2,2,6,6-tetrannethy1-4-piperidyl)]siloxane, a reaction product of nnaleic acid anhydride-oc-olefin copolymer with 2,2,6,6-tetrannethy1-4-anninopiperidine or 1,2,2,6,6-pentannethy1-4-anninopiperidine, 2,4-bis[N-(1-cyclohex-yloxy-2,2,6,6-tetrannethylpiperidine-4-y1)-N-butylannino]-6-(2-hydroxyethyl)annino-1,3,5-triazine, 1-(2-hydroxy-2-nnethylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetrannethylpiperi-dine, 5-(2-ethylhexanoyDoxynnethyl-3,3,5-trimethyl-2-nnorpholinone, Sanduvor (Clariant;
CAS Reg. No. 106917-31-1], 5-(2-ethylhexanoyl)oxynnethyl-3,3,5-trinnethyl-2-nnorpho-linone, the reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butyla-nnino]-6-chloro-s-triazine with N,N'-bis(3-anninopropyl)ethylenediannine), 1,3,5-tris(N-cy-clohexyl-N-(2,2,6,6-tetrannethylpiperazine-3-one-4-yDamino)-s-triazine, 1,3,5-tris(N-cy-clohexyl-N-(1,2,2,6,6-pentannethylpiperazine-3-one-4-yl)annino)-s-triazine.
2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dinnethylanninopropyl)oxannide, 2-ethoxy-5-tert-buty1-2'-ethox-anilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-nnethoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxani-lides.
2.8. 2-(2-Hydroxypheny1)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxy-phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyI)-4,6-bis(2,4-dinnethylpheny1)-1,3,5-triazine, 2-(2,4-dihydroxyphenyI)-4,6-bis(2,4-dinnethylpheny1)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyI)-6-(2,4-dinnethylpheny1)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxypheny1)-4,6-bis(4-nnethylpheny1)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxy-pheny1)-4,6-bis(2,4-dinnethylpheny1)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyI)-4,6-bis(2,4-dinnethylphenyI)-1,3,5-triazine, 242-hydroxy-4-(2-hydroxy-3-butyloxypro-poxy)pheny1]-4,6-bis(2,4-dinnethyl)-1,3,5-triazine, 242-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)pheny1]-4,6-bis(2,4-dinnethyl)-1,3,5-triazine, 2-[4-(do-decyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxypheny1]-4,6-bis(2,4-dinnethylpheny1)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)pheny1]-4,6-bis(2,4-di-nnethylpheny1)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)pheny1-4,6-dipheny1-1,3,5-tria-5 zine, 2-(2-hydroxy-4-nnethoxypheny1)-4,6-dipheny1-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)pheny1]-1,3,5-triazine, 2-(2-hydroxypheny1)-4-(4-nnethoxy-pheny1)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexy1-1-oxy)-2-hydroxypropy-loxy]pheny1}-4,6-bis(2,4-dinnethylpheny1)-1,3,5-triazine, 2 ,4-bis(4-[2-ethylhexyloxy]-2-hy-droxypheny1)-6-(4-nnethoxypheny1)-1,3,5-triazine, 2,4-bis(4-biphenyly1)-6-[2-hydroxy-4-10 (2-ethylhexyloxy)phenyl] -1,3,5-triazine.
3. Metal deactivators, for example N,N'-diphenyloxannide, N-salicylal-N'-salicyloyl hydra-zine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-buty1-4-hydroxyphenylpropio-nyl)hydrazine, 3-salicyloylannino-1,2,4-triazole, bis(benzylidene)oxaly1 dihydrazide, 15 oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyDoxalyldihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihy-drazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phos-20 phites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, triocta-decyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phos-phite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cunnylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-buty1-4-nnethylphenyOpentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, 25 bis(2,4-di-tert-butyl-6-nnethylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-bu-tylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-buty1-1 2H-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-nnethylphenyl)nnethyl phos-phite, bis(2,4-di-tert-buty1-6-nnethylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, 2,2',2"-nitrilo[triethyltris(3,3',5,5'-tetra-tert-buty1-1,1'-bipheny1-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5 ,5'-tetra-tert-butyl-1,1'-bipheny1-2,2'-diyl)phosphite, 5-buty1-5-ethy1-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-di-oxaphosphirane, phosphorous acid, mixed 2,4-bis(1,1-dinnethylpropyl)phenyl and 4-(1, 1-dinnethylpropyl)phenyl triesters (CAS: 939402-02-5)., phosphorous acid, triphenyl es-ter, polymer with a-hydro-w-hydroxypoly[oxy(nnethy1-1,2-ethanediy1)], C10-16-alkyl es-ters (CAS: 1227937-46-3).

The following phosphites are especially preferred:
Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos'168, Ciba Specialty Chemicals Inc.), tris(nonylphenyl) phosphite, (CH3)3C C(C H3)3 (CH3)3C C(CH3)3 (A) H3C ¨CH P¨ F p __ 0 __ CH,CH, N (B) (CH3)3C
C (CH3)3 C(CH3)3 (CH3)3C ¨ 3 C(CH3)3 (CH3)3C

(C) P CH2C H(C4H9) CH2CH3 (CH3)3C
C(CH,), 0\
(CH3)3C Px P ¨ 0 C(CH3)3 \ID (D) C(CH3)3 (CH3)3C
C(CH3)3 (CH3)3C
0\
H3C 0 __ Px P ¨ 0 CH3 (E) C(CH3)3 (CH3)30 (F) H37C18 _______________ 0 __ P \P 0 C18H37 CH, H3C ¨C ¨CH3 0 ________________________________________________ P OCH2CH3 (G) H3C '.CH, ¨ 2 5. Hydroxylamines, for example N,N-dibenzylhydroxylannine, N,N-diethylhydroxylannine, N,N-dioctylhydroxylannine, N,N-dilaurylhydroxylannine, N,N-ditetradecylhydroxylannine, N,N-dihexadecylhydroxylannine, N,N-dioctadecylhydroxylannine, N-hexadecyl-N-octade-cylhydroxylannine, N-heptadecyl-N-octadecylhydroxylannine, N,N-dialkylhydroxylannine derived from hydrogenated tallow amine.
6. Nitrones, for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-nnethylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnit-rone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptade-cyl-alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylannine derived from hydrogenated tallow amine.
7. Thiosynergists, for example dilauryl thiodipropionate, dinnistryl thiodipropionate, dis-tearyl thiodipropionate or distearyl disulfide.
8. Peroxide scavengers, for example esters of p-thiodipropionic acid, for example the lauryl, stearyl, nnyristyl or tridecyl esters, nnercaptobenzinnidazole or the zinc salt of 2-nnercaptobenzinnidazole, zinc dibutyldithiocarbannate, dioctadecyl disulfide, pentaeryth-ritol tetrakis(p-dodecylnnercapto)propionate.
9. Polyannide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiannide, tri-ally! cyanurate, urea derivatives, hydrazine derivatives, amines, polyannides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palnnitate, antimony pyrocatecholate or zinc pyrocate-cholate.
11. Nucleating agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (iononners). Especially preferred are 1,3:2,4-bis(3',4'-dinnethylbenzylidene)sorbitol, 1,3:2,4-di(parannethyldibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol.
12. Fillers and reinforcing agents, for example calcium carbonate, silicates, surface treated silica (as described e.g. in US-A-2007/60,697 and US-A-2009/111,918), glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hy-droxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
13. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flanneproofing agents, anti-static agents and blowing agents.
14. Benzofuranones and indolinones, for example those disclosed in U.S.
4,325,863;
U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611;
DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384 or 344-(2-acetoxyethoxy)phenyI]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-buty1-344-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-buty1-3-(4-[2-hydroxy-ethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-buty1-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dinnethylphenyI)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dime-thy1-4-pivaloyloxypheny1)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyI)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dinnethylphenyI)-5,7-di-tert-butylbenzofuran-2-one, 3-(2-acetyl-5-isooctylpheny1)-5-isooctylbenzofuran-2-one.

The weight ratio of the present stabilizer mixture to the total amount of the conventional additive(s) can be for example 100:1 to 1:1000 or 10:1 to 1:100 or 20 to 1 to 1 to 20 or 10:1 to 1:10.
A further embodiment of the present invention is a composition which additionally con-tains a further additive selected from the group consisting of antioxidants, slip agents, anti-block agents, thermal fillers, pigments, anti-fog and anti-mist agents.
The materials stabilized according to this invention can be used in a wide va-riety of forms, for example as films, fibres, tapes, moulding compositions, pro-files or as binders for paints, adhesives or putties.
In more detail, the materials stabilized according to the present invention may be used for the preparation of the following devices:
1-1) Automotive applications, in particular bumpers, dashboards, battery, rear and front linings, moldings parts under the hood, hat shelf, trunk linings, interior linings, air bag covers, electronic moldings for fittings (lights), panes for dashboards, headlamp glass, instrument panel, exterior linings, upholstery, automotive lights, head lights, parking lights, rear lights, stop lights, interior and exterior trims; door panels;
gas tank; glazing front side; rear windows; seat backing, exterior panels, wire insulation, profile extrusion for sealing, cladding, pillar covers, chassis parts, exhaust systems, fuel filter! filler, fuel pumps, fuel tank, body side mouldings, convertible tops, exterior mirrors, exterior trim, fasteners / fixings, front end module, glass, hinges, lock systems, luggage!
roof racks, pressed/stamped parts, seals, side impact protection, sound deadener /
insulator and sunroof.
1-2) Devices for plane, railway, motor car (car, motorbike) including furnishings.
1-3) Devices for space applications, in particular rockets and satellites, e.g. reentry shields.
1-4) Devices for architecture and design, mining applications, acoustic quietized systems, street refuges, and shelters.

11-1) Electric appliances, in particular washing machines, tumblers, ovens (microwave oven), dish-washers, mixers, and irons.
11-2) Foils for condensers, refrigerators, heating devices, air conditioners, encapsulating 5 of electronics, semi-conductors, coffee machines, and vacuum cleaners.
111-1) Technical articles such as cogwheel (gear), slide fittings, spacers, screws, bolts, handles, and knobs.
10 111-2) Rotor blades, ventilators and windmill vanes, solar devices, swimming pools, swim-ming pool covers, pool liners, pond liners, closets, wardrobes, dividing walls, slat walls, folding walls, roofs, shutters (e.g. roller shutters), fittings, connections between pipes, sleeves, and conveyor belts.
15 111-3) Profiles of any geometry (window panes) and siding.
111-4) Glass substitutes, in particular extruded plates, glazing for buildings (monolithic, twin or nnultiwall), aircraft, schools, extruded sheets, window film for architectural glazing, train, transportation, sanitary articles, and greenhouse.
111-5) Plates (walls, cutting board), extrusion-coating (photographic paper, tetrapack and pipe coating), silos, wood substitute, plastic lumber, wood composites, walls, surfaces, furniture, decorative foil, floor coverings (interior and exterior applications), flooring, duck boards, and tiles.
111-6) Cement-, concrete-, composite-applications and covers, siding and cladding, hand rails, banisters, kitchen work tops, roofing, roofing sheets, tiles, and tarpaulins.
1V-1) Plates (walls and cutting board), trays, artificial grass, astroturf, artificial covering for stadium rings (athletics), artificial floor for stadium rings (athletics), and tapes.
V-1) Plastic films in general (packaging, dump, laminating, swimming pools covers, waste bags, wallpaper, stretch and shrink wrap, raffia, desalination film, batteries, and connectors).

V-2) Agricultural films (greenhouse covers, tunnel, mulch, silage, bale wrap), especially in presence of intensive application of agrochemicals).
VI-1) Food packing and wrapping (flexible and solid), BOPP, BOPET, bottles.
VI-2) Cartridges, syringes, medical applications, containers for any transportation, waste baskets and waste bins, waste bags, bins, dust bins, bin liners, wheely bins, container in general, tanks for water / used water / chemistry / gas / oil / gasoline /
diesel; tank liners, boxes, crates, battery cases, troughs, medical devices such as piston, ophthalmic applications, diagnostic devices, and packing for pharmaceuticals blister.
VII-1) Devices of filled polymers (talc, chalk, china clay (kaolin), wollastonite, pigments, carbon black, TiO2, mica, nanoconnposites, dolomite, silica, silicates, glass, asbestos).
Thus, another embodiment of the present invention is an article made of a composition as described above. A plastic article for agricultural use, preferably a thin film, typically obtained with the blow extrusion technology, is preferred. A monolayer film or a multilayer film of three, five or seven layers, preferably of a thickness of 180 microns or 120 mi-crons, typically 60 to 100 microns, is of particular interest. The most important application of thin plastic films in agriculture is as covers for greenhouses and tunnels to grow crops in a protected environment.
A multilayer film, preferably a multilayer polyolefin film, in particular a multilayer polyeth-ylene film, which contains a compound of the formula (A) in at least one layer and a compound of the formula (B) in another layer, is also preferred.
Such a multilayer film is typically made of three, five or seven layers. This can lead to a filrinstructurelikeABA,ABC,ABCBA,ABCBD,ABCDCBAor AABCBA A. A, B, C, D represent the different polymers and tackifiers mentioned in the following.
However, adjacent layers can also be coupled so that the final film article can be made of an even number of layers, i.e. two, four or six layers such as A-A-B-A, A-A-B-B, A-A-B-A-A, A-B-B-A-A, A-A-B-C-B, A-A-B-C-A-A and the like.
32 The thin films containing one of the aforementioned light stabilizers are typically made of low density polyethylene (from radical polymerization or of the linear type), linear low density polyethylene, nnetallocene linear low density polyethylene , C4-LLDPE, LLDPE, medium density polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl acrylate copoly-mer, and combinations thereof, of polypropylene, (either honno- and co-polymer) or of high density polyethylene. This can include nnultilayers of the same polymer type with different viscosity or co-monomer content (e.g. vinyl-acetate content) or virgin polymer and regrind or recyclate. This can include a strength layer of polyannide 6 and polyannide 6.6 or tie layers of polyisobutylene, nnaleic anhydride grafted polyethylene, nnaleic anhy-dride grafted polypropylene or a layer of biodegradable resins. Such combinations are optimized for example to maximize the initial mechanical properties (tensile strength, puncture resistance, impact resistance, elongation properties) of the plastic article, im-prove inter-layer adhesion strength or to achieve special functionalities (gas barrier prop-erties, transparency, heat seal properties) of the same.
The stabilizer mixture according to the present invention is particularly useful for stabiliz-ing greenhouse film covers, which are in contact with an agrochemical compound such as e.g. Metam-Sodium (Sodium N-nnethyldithiocarbamate), Cymoxanil (2-Cyan-N-[(ethylannino)carbony1]-2-(nnethoxyinnino)acetannide), Thirann (Bis(dinnethylthiocar-bannoyDdisulfide), Mancozeb (Mn-Zn-ethylenebis(dithiocarbannate)) or elemental sulfur, in particular elemental sulfur or Metam-Sodium.
Thus, a further embodiment of the present invention is a greenhouse film cover which is in contact with an agrochemical compound.
Still a further embodiment of the present invention is a method for stabilizing an organic material, preferably an organic polymer, against degradation induced by light, heat, oxi-dation or the effect of agrochemical compounds, which comprises incorporating into the organic material a stabilizer mixture as defined above.
The following examples illustrate the invention in greater detail. All percentages and parts are by weight, unless stated otherwise.
Examples:
33 Stabilizers listed in Tables 1 to 4 below:
Compound (A-3-1):

C4H, H9C 4¨N N N
___________________________ N __ (CH2)6 __________ N ____ N ______ (C H2)6 N
¨C4H6 N ,N N ,N
H9c4 H3C cH,H3c jCH3 H3c cH,H3c1, ,tcH, H3c c3 HC N CH3 HgC4¨N H3C N

C4Hg H3C.õ1 11j_chi3 H3C1 'CH3 a wherein a is a number from 1 to 10.
Compound (A-4-1):

HgC4¨N N N, __ N (CH2)6 N r N ___ (CH2)6 N __ rN
N¨C4H9 N N N N
HgC4 N
I-13C C1-131-13C CH3 HgC TH3C,,1 CH3H3C

I
N CH3 __ N C41-10 13C I1 'I' CH3 H3C NI CI 13 4¨N H3c C4 Fig H3C 1\111 CH3 ¨ a wherein a is a number from 1 to 10.
Compound (B-1):
0-CH)-C4H9-n OH
N N
Compound (B-2):
34 0 __________________________ C8H13-n OH
N N
Compound (B-3):
0¨C8H17 OH
N N

Compound (C):
9 'H
C
CtHi7 Compound (D-1):

H3C C CH2 0 NI\ 2 0 -C -Ci7H35 Compound (D-2):
(Tinuvin 622) H3c cH3 Y
--( ________________________ /
/ \

wherein b is a number from 2 to 10.
5 Application Examples 1 to 7 A) Preparation of film samples:
Stabilization of LDPE (low density polyethylene) multi-layer films:
Formulations contain-ing LDPE powder (Polinneri Europa Riblene FC 30, characterized by a density of 0.922 10 g/cm3 and a melt flow index (190 C/2.16Kg) of 0.27 g/10min), 0.04% by weight, relative to the weight of the LDPE, of tris{2,4-di-tert-butylphenyl} phosphite, 0.01%
by weight, relative to the weight of the LDPE, of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)pro-pionate and the stabilizer mixtures indicated in Tables 1 and 2 are prepared.
The formu-lations are mixed in a turbo-mixer. Each formulation is extruded at a maximum temper-15 ature of 200 C in a lab-scale single-screw Collin extruder (0 42nnnn, L/D=25). Then, each final formulation is blown in a lab-scale Collin 5-layer blow-extruder (0 20-25-30nnm, L/D 25), at a maximum temperature of 210 C, to give a 5-layer film having the same formulation in all layers. The overall thickness of the film was 1601.1m (50 m ¨ 15 1.1rin ¨
30 m ¨15 ..irn - 50 m ).
B) Test method An agrochemical treatment is carried out on the prepared films before artificial weather-ing. Specimens of the films for each formulation are mounted on a small experimental greenhouse (geographical coordinates: Lat. 44 25'40"N Long.11 16'39"E), inside of which two burners of the type used in common agricultural practice are placed to allow sublimation of elemental sulfur, a widely used fungicide. The so-called "sulfur burning" is carried out for 13 consecutive days, 6 hours per day, while the films are mounted on the small experimental greenhouse. The film specimens are covered with an additional sin-gle piece of opaque film to minimize the direct exposure of the sample to sunlight, in order to minimize in turn the effects of solar irradiation and hence the possible differences on samples exposed in subsequent test series. The amount of burnt sulfur is regulated and the weathering conditions closely monitored, so as to obtain the desired level of contamination from sulfur in the film samples, measured by Inductively Coupled Plasma.
After the agrochemical treatment, the film specimens for each formulation are exposed in an Atlas Weather-O-Meter (WOM, as per ASTM G155, 0.35 Winn2 at 340 nnn, dry cycle), for accelerated light weathering. Specimens of the film samples are taken at de-fined intervals of time after exposure and underwent tensile testing. The residual tensile strength is measured, by means of a Zwick Z1.0 constant velocity tensiometer (as per modified ISO 527), in order to evaluate the decay of the mechanical properties of the film samples, as a consequence of the polymer degradation after its oxidation.
The test results are listed in Tables 1 and 2.
Table 1:
Film samples contaminated up to level of sulfur of 5000 ppm and exposed in a WOM.
Stabilizer mixture (weight-% Retained elongation at break (as based on polymer composition) % of initial) after 4000 hours WOM treatment Example 1 0.550% of Compound (A-4-1) 6.4 (Comparative) 0.064% of Compound (C) Example 2 0.550% of Compound (A-4-1) 0.015% of Compound (B-1) 77.1 0.049% of Compound (C) Example 3 0.550% of Compound (A-4-1) 0.015% of Compound (B-2) 78.9 0.049% of Compound (C) Example 4 0.550% of Compound (A-4-1) 0.015% of Compound (B-3) 69.4 0.049% of Compound (C) High values are desired.
Table 2:
Film samples contaminated up to level of sulfur of 5000 ppm and exposed in a WOM.

Stabilizer mixture (weight-% Retained elongation at break (as based on polymer composition) % of initial) after 4000 hours WOM treatment Example 5 0.350% of Compound (A-4-1) (Comparative) 0.050% of Compound (D-1) 61.8 0.150% of Compound (D-2) 0.064% of Compound (C) Example 6 0.350% of Compound (A-4-1) 0.050% of Compound (D-1) 0.150% of Compound (D-2) 88.2 0.049% of Compound (C) 0.015 of Compound (B-1) Example 7 0.350% of Compound (A-4-1) 0.050% of Compound (D-1) 0.150% of Compound (D-2) 79.7 0.049% of Compound (C) 0.015 of Compound (B-3) High values are desired.
Application Examples 8 to 11 A) Preparation of film samples:
Preparation of stabilized LDPE (low density polyethylene) / LLDPE (linear low density polyethylene) / EVA (ethylene-vinyl acetate copolymer) multi-layer film samples:
Concentrated formulations containing in total 20% of the stabilizer mixtures indicated in Tables 3 and 4 below, LDPE powder (Polinneri Europa Riblene FC 30, characterized by a density of 0.922 g/crin3 and a melt flow index (190 C/2.16Kg) of 0.27 g/10nnin), 0.04%
by weight, relative to the weight of the LDPE, of tris{2,4-di-tert-butylphenyl} phosphite, 0.01% by weight, relative to the weight of the LDPE, of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are prepared. The formulations are mixed in a turbo-mixer.
Each formulation is extruded at a maximum temperature of 200 C in a lab-scale double-screw Connac extruder (0 34nnnn, L/D=32). Then, the concentrates are blown in an in-dustrial-scale 3-layer blow-extruder (0 20-25-30nnnn, LJD 25), at a maximum temperature of 210 C to the final formulations indicated in Tables 3 and 4, by dosing the appropriate amounts of each concentrated formulation and a mixture of the following polymers: 66%

of Pofinned Europa Riblene FF30, 19% of Exxon Enable 2005HH and 15% of Polinneri Europa Greenflex F045. The produced 3-layer films have the same composition of the polymer mixtures in all layers and, as a result, of the stabilization composition. The over-all thickness of the films is 1501.tm (45 601.1m ¨ 45 m) for Test method B1 and 200 lam (60 j.trin¨ 801.tm ¨ 601.tm) for Test method B2.
B1) Test method Specimens of the films for each formulation are placed on the roof of an experimental greenhouse (geographical coordinates: Lat. 44 25'40"N Long.11 16'39"E) facing the South and wherein spraying with agrochemicals can be carried out, mounted on frames made in such a way that the specimen is in direct contact with a metal (galvanized iron) bar, simulating the contact with metallic supports in a real greenhouse.
Treatments with Funnathane 510, a sulfur-based broad-spectrum fumigant, and with Pertrin S, a chlorine-based insecticide, are performed, respectively twice per year and monthly.
Specimens of the film samples in contact with the metal are taken at defined intervals of time after exposure and undergo tensile testing. The residual tensile strength is meas-ured, by means of a Zwick Z1.0 constant velocity tensiometer (as per modified ISO
527), in order to evaluate the decay of the mechanical properties of the film samples, as a consequence of the polymer degradation after its oxidation.
The test results are listed in Table 3.
Table 3:
Film samples exposed outdoor and contaminated up to level of sulfur of 3000 ppm.
Stabilizer mixture (weight-% Retained elongation at break on based on polymer composition) galvanized iron after specified solar irradiation Example 8 0.30% of Compound (A-3-1) Not measurable, because brittle (Comparative) 0.30% of Compound (A-4-1) after 10.8 GJ/nn2 0.05% of Compound (B-1) Example 9 0.30% of Compound (A-3-1) 0.30% of Compound (A-4-1) 100% after 16 GJ/rin2 0.02% of Compound (B-1) 0.30% of Compound (C) High elongation value after more irradiation is desired B2) Test method Specimens of the films for each formulation are placed on the roof of a small experi-mental greenhouse (geographical coordinates: Lat. 44 25'40"N Long.11 16'39"E) facing the South and inside of which a burner of the type used in common agricultural practice is placed, to allow sublimation of elemental sulfur, a widely used fungicide.
The burner is operated every day of the exposure for three hours overnight.
Specimens of the film samples are taken at defined intervals of time after exposure and undergo tensile testing. The residual tensile strength is measured, by means of a Zwick Z1.0 constant velocity tensiometer (as per modified ISO 527), in order to evaluate the decay of the mechanical properties of the film samples, as a consequence of the polymer degradation after its oxidation.
The test results are listed in Table 4.
Table 4:
Film samples exposed outdoor and contaminated up to level of sulfur of 15000 ppm.
Stabilizer mixture (weight-% Solar irradiation to 30% of the in-based on polymer composition) itial elongation at break Example 10 1.20% of Compound (A-4-1) 9.2 GJ/rin2 (Comparative) 0.15% of Compound (B-1) Example 11 1.20% of Compound (A-4-1) 0.05% of Compound (B-1) 9.4 GJ/rin2 0.30% of Compound (C) High solar irradiation value is desired

Claims (15)

Claims:
1. A stabilizer mixture comprising the components (a), (b) and (c), wherein component (a) is at least one compound of the formula (A), wherein A1 is 02-C18alkylene, Cs-C7cycloalkylene or Ci-C4alkylenedi(Cs-C7cycloal-kylene), the radicals A2 independently of one another are hydrogen, Ci-Cualkyl, Ci-Ci2alkyloxy, C5-Cucycloalkyl or C5-Cucycloalkyloxy, A3 and Azi independently of one another are hydrogen, Ci-Ci2alkyl, 05-Ci2cycloalkyl or a group of the formula (a-1), or the radicals A3 and Azi, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, and a is a number from 1 to 20 and the repeating units are identical or different;
component (b) is at least one compound selected from the formulae (B-l) and (B-ll), wherein E2, E3, E4 and E5 independently of one another are hydrogen, Ci-Ci8alkyl, phenyl or phenyl substituted by 1, 2 or 3 Ci-C4alkyl;
n is 1 or 2, when n is 1, Ei is Ci-Ci8alkyl, or C2-Ci8hydroxyalkyl which is interrupted by oxygen, and when n is 2, Ei is a bridging group of formula -CH2CH2-0-C(0)-(CH2)10-C(0)-0-CH2CH2-, wherein Qi, Qz, Q3 and Q4 are independently of one another hydrogen, Ci-Ci8alkyl, Ci-Cisalkyl substituted by hydroxy, C2-C18alkyl or C2-Ci8hydroxyalkyl interrupted by oxygen, and Ti , T2 and T3 are independently from each other hydrogen or Ci-Ci8alkyl;
component (c) is a compound of formula (C) and wherein the weight ratio of component (b) to (c) is 1:50 to 50:1.
2. A stabilizer mixture according to claim 1, wherein A1 is 02-C8alkylene or cyclohexylene, the radicals A2 independently of one another are hydrogen, Ci-Coalkyl, Ci-Ci2alkyloxy, cyclohexyl or cyclohexyloxy, A3 and A4 independently of one another are hydrogen, Ci-Coalkyl or a group of the for-mula (a-1), and a is a number from 1 to 10.
3. A stabilizer mixture according to claim 1 or 2, wherein E2, E3, E4 and E5 are independently from each other hydrogen, Cl-Caalkyl or phenyl, Q2, Q3 and Q4 are independently from each other hydrogen or Ci-Cioalkyl, and T1, T2 and T3 are independently from each other hydrogen or Ci-C4alkyl.
4. A stabilizer mixture according to any of claims 1 to 3, wherein component (a) is at least one compound selected from the formulae (A-0), (A-1), (A-2), (A-3), (A-4) and (A-5) wherein 1 or 2 of the radicals A2 are hydrogen and the remaining radicals A2 are propyloxy, wherein a is a number from 1 to 20;
wherein a is a number from 1 to 20.
5. A stabilizer mixture according to any of claims 1 to 4, wherein component (b) is at least one compound selected from the formulae (B-1), (B-2) and (B-3)
6. A stabilizer mixture according to any of claims 1 to 5, which additionally comprises component (d) which is at least one compound selected from the formulae (D-1) and (D-2) wherein b is a number from 2 to 20.
7. A composition comprising (l) an organic material subject to degradation induced by light, heat, oxidation or agro-chemical compounds and (11) a stabilizer mixture as defined in claim 1.
8. A composition according to claim 7, wherein the organic material is a polyolefin.
9. A composition according to claim 7 or 8, which additionally comprises a further additive selected from the group consisting of antioxidants, slip agents, anti-block agents, thermal fillers, pigments, anti-fog and anti-mist agents.
10. An article made of a composition according to claim 7.
11. An article according to claim 10, which is a monolayer film or a multilayer film of three to seven layers.
12. An article according to claim 10, which is a multilayer film, preferably a polyolefin film, which comprises a compound of the formula (A) as defined in claim 1 in at least one layer and a compound of the formula (B-l) or (B-ll) as defined in claim 1 in another layer.
13. An article according to claim 10, which is a greenhouse film cover.
14. An article according to claim 13, characterized in that the greenhouse film cover is in contact with an agrochemical compound.
15. A method for stabilizing an organic material against degradation induced by light, heat, oxidation or the effect of agrochemical compounds, which comprises incorporating into the organic material a stabilizer mixture as defined in claim 1.
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